Method to make alkanes and saturated polyhydroxy compounds from carbonyl compounds

Abstract

A catalytic process for converting biomass-derived carbohydrates to liquid alkanes, alkenes, and/or ethers is described. The process uses combinations of self- and crossed-aldol condensation reactions, dehydration reactions, and hydrogenation reactions, over specified metal-containing catalysts, to yield alkane, alkene, and ether products from carbohydrate reactants.

1. A method for making alkanes comprising, in an aqueous reaction solution:
 (a) subjecting a carbonyl compound to at least one self-aldol condensation reaction or a crossed-aldol condensation reaction with another carbonyl compound to yield a beta-hydroxy carbonyl compound and/or an alpha-beta unsaturated carbonyl compound; then 
 (b) hydrogenating the beta-hydroxy carbonyl and/or alpha-beta unsaturated compounds to yield a saturated polyhydroxy compound; and then 
 (c) dehydrating and hydrogenating the saturated polyhydroxy compound to yield a C 6  to C 15  alkane that is immiscible in the aqueous reaction solution. 
 
     
     
       2. The method of  claim 1 , wherein step (a) further comprises running the self-aldol condensation reaction or the crossed-aldol condensation reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen. 
     
     
       3. A method for making alkanes comprising, in an aqueous reaction solution:
 (a) reducing a carbohydrate reactant to yield at least one carbonyl compound having an alpha-position hydrogen; then 
 (b) subjecting the carbonyl compound to at least one self-aldol condensation reaction or a crossed-aldol condensation reaction with another carbonyl compound to yield a beta-hydroxy carbonyl compound and/or an alpha-beta unsaturated carbonyl compound; then 
 (c) hydrogenating the beta-hydroxy carbonyl and/or the alpha-beta unsaturated carbonyl compounds to yield a saturated polyhydroxy compound; and then 
 (d) dehydrating and hydrogenating the saturated polyhydroxy compound to yield an alkane that is immiscible in the aqueous reaction solution. 
 
     
     
       4. The method of  claim 3 , wherein in step (a) the carbohydrate reactant is a sugar. 
     
     
       5. The method of  claim 3 , wherein in step (a), the carbohydrate reactant is derived from biomass. 
     
     
       6. The method of  claim 3 , wherein step (b) comprises running the self-aldol condensation reaction or the crossed-aldol condensation reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen. 
     
     
       7. A method for making alkanes comprising, in an aqueous reaction solution:
 (a) dehydrating a C 6  sugar to yield hydroxymethylfurfural; then 
 (b) subjecting the hydroxymethylfurfural to at least one crossed-aldol condensation reaction with an aldehyde or a ketone to yield a beta-hydroxy carbonyl and/or an alpha-beta unsaturated carbonyl having at least seven (7) carbon atoms; then 
 (c) hydrogenating the beta-hydroxy carbonyl and/or alpha-beta unsaturated carbonyl to yield a saturated polyhydroxy compound; and then 
 (d) dehydrating and hydrogenating the saturated polyhydroxy compound to yield an alkane having at least seven (7) carbon atoms. 
 
     
     
       8. The method of  claim 7 , wherein in step (a),the C 6  sugar is derived from biomass. 
     
     
       9. The method of  claim 7 , wherein step (b) yields a beta -hydroxy carbonyl and/or an alpha-beta unsaturated carbonyl having at least nine (9) carbon atoms; and step (d) yields an alkane having at least nine (9) carbon atoms. 
     
     
       10. The method of  claim 7 , wherein step (b) yields a beta -hydroxy carbonyl and/or an alpha-beta unsaturated carbonyl having at least eleven (11) carbon atoms; and step (d) yields an alkane having at least eleven (11) carbon atoms. 
     
     
       11. The method of  claim 7 , wherein step (b) yields a beta-hydroxy carbonyl and/or an alpha-beta unsaturated carbonyl having at least thirteen (13) carbon atoms; and step (d) yields an alkane having at least thirteen (13) carbon atoms. 
     
     
       12. The method of  claim 7 , wherein step (b) yields a beta-hydroxy carbonyl and/or an alpha-beta unsaturated carbonyl having at least fifteen (15) carbon atoms; and step (d) yields an alkane having at least fifteen (15) carbon atoms. 
     
     
       13. The method of  claim 7 , wherein step (b) comprises running the self-aldol condensation reaction or the crossed-aldol condensation reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen. 
     
     
       14. A method for making alkanes comprising, in an aqueous reaction solution:
 (a) dehydrating a C 6  sugar to yield hydroxymethylfurfural; then 
 (b) hydrogenating the hydroxymethylfurfural to yield hydroxymethyltetrahydrofurfural; then 
 (c) subjecting the hydroxymethyltetrahydrofurfural to a self-aldol condensation reaction to yield a C 12  beta-hydroxy ketone and/or a C 12  alpha-beta unsaturated ketone; then 
 (d) hydrogenating the C 12  beta-hydroxy ketone and/or the C 12  alpha-beta unsaturated ketone to yield a saturated polyhydroxy compound; and then 
 (e) dehydrating and hydrogenating the saturated polyhydroxy compound to yield a C 12  alkane. 
 
     
     
       15. The method of  claim 14 , wherein step (c) comprises running the self-aldol condensation reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen. 
     
     
       16. A method for making alkanes comprising, in an aqueous reaction solution:
 (a) dehydrating a C 6  sugar to yield hydroxymethylfurfural; then 
 (b) subjecting the hydroxymethyltetrahydrofurfural to a first crossed-aldol condensation reaction with a first carbonyl compound having an alpha-position hydrogen, and then a second crossed-aldol condensation reaction with a second carbonyl compound lacking an alpha-position hydrogen, to yield a di-(beta-hydroxy) carbonyl and/or a di-(alpha-beta unsaturated) carbonyl having at least ten (10) carbon atoms; then 
 (c) hydrogenating the di-(beta-hydroxy) carbonyl and/or the di-(alpha-beta unsaturated) carbonyl to yield a saturated polyhydroxy compound; and then 
 (d) dehydrating and hydrogenating the polyhydroxy compound to yield an alkane having at least ten (10) carbon atoms. 
 
     
     
       17. The method of  claim 16 , wherein in step (b) the first carbonyl compound is acetone, and the second carbonyl compound is hydroxymethylfurfural. 
     
     
       18. The method of  claim 16 , wherein step (b) comprises running the first crossed-aldol condensation reaction and the second crossed-aldol reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen. 
     
     
       19. A method for making to C 1  to C 15  alkanes comprising, in an aqueous reaction solution:
 (a) subjecting a carbonyl compound to at least one self -aldol condensation reaction or a crossed-aldol condensation reaction with another carbonyl compound to yield a beta-hydroxy carbonyl compound and/or an alpha-beta unsaturated carbonyl compound; then 
 (b) hydrogenating the beta-hydroxy carbonyl and/or alpha-beta unsaturated compounds to yield a saturated polyhydroxy compound; and then 
 (c) dehydrating and hydrogenating the saturated polyhydroxy compound to yield a C 1  to C 15  alkane. 
 
     
     
       20. The method of  claim 19 , wherein step (a) further comprises running the self-aldol condensation reaction or the crossed-aldol condensation reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen. 
     
     
       21. A method for making alkanes comprising, in an aqueous reaction solution:
 (a) dehydrating a C 5  sugar to yield furfural; then 
 (b) subjecting the furfural to at least one crossed-aldol condensation reaction with an aldehyde or a ketone to yield a beta-hydroxy carbonyl and/or an alpha-beta unsaturated carbonyl having at least six (6) carbon atoms; then 
 (c) hydrogenating the beta-hydroxy carbonyl and/or alpha-beta unsaturated carbonyl to yield a saturated polyhydroxy compound; and then 
 (d) dehydrating and hydrogenating the saturated polyhydroxy compound to yield an alkane having at least six (6) carbon atoms. 
 
     
     
       22. A method for making alkanes comprising, in an aqueous reaction solution:
 (a) dehydrating a C 5  sugar to yield furfural; then 
 (b) subjecting the furfural to a first crossed-aldol condensation reaction with a first carbonyl compound having an alpha-position hydrogen, and then a second crossed-aldol condensation reaction with a second carbonyl compound lacking an alpha-position hydrogen, to yield a di-(beta-hydroxy) carbonyl and/or a di-(alpha-beta unsaturated) carbonyl having at least nine (9) carbon atoms; then 
 (c) hydrogenating the di-(beta-hydroxy) carbonyl and/or the di-(alpha-beta unsaturated) carbonyl to yield a saturated polyhydroxy compound; and then 
 (d) dehydrating and hydrogenating the polyhydroxy compound to yield an alkane having at least eight (8) carbon atoms. 
 
     
     
       23. A method for making alkanes comprising, in an aqueous reaction solution:
 (a) subjecting tetrahydrofurfural to a self-aldol condensation reaction to yield a C 10  beta-hydroxy ketone and/or a C 10  alpha-beta unsaturated ketone; then 
 (b) hydrogenating the C 10  beta-hydroxy ketone and/or the C 10  alpha-beta unsaturated ketone to yield a saturated polyhydroxy compound; and then 
 (c) dehydrating and hydrogenating the saturated polyhydroxy compound to yield a C 10  alkane. 
 
     
     
       24. A method for making organic polyhydroxy compounds comprising, in an aqueous reaction solution:
 (a) subjecting a carbonyl compound to at least one self -aldol condensation reaction or a crossed-aldol condensation reaction with another carbonyl compound to yield a beta-hydroxy carbonyl compound and/or an alpha-beta unsaturated carbonyl compound; then 
 (b) hydrogenating the beta-hydroxy carbonyl and/or alpha-beta unsaturated compounds to yield a polyhydroxy compound. 
 
     
     
       25. The method of  claim 24 , wherein in step (b) the beta -hydroxy carbonyl and/or alpha-beta unsaturated compounds are hydrogenated such that the polyhydroxy compound is a saturated polyhydroxy compound. 
     
     
       26. The method of  claim 25 , further comprising, after step (b):
 (c) dehydrating and hydrogenating the saturated polyhydroxy compound to yield a C 6  to C 15  alkane that is immiscible in the aqueous reaction solution. 
 
     
     
       27. The method of  claim 24 , further comprising, after step (b):
 (c) dehydrating the saturated polyhydroxy compound to yield a C 6  to C 15  alkene or ether. 
 
     
     
       28. The method of  claim 24 , wherein step (a) further comprises running the self-aldol condensation reaction or the crossed-aldol condensation reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen.